JP4427109B2 - Phosphorane and diphosphorane, metal complexes thereof, use thereof and method of asymmetric hydrogenation - Google Patents

Phosphorane and diphosphorane, metal complexes thereof, use thereof and method of asymmetric hydrogenation Download PDF

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JP4427109B2
JP4427109B2 JP17112998A JP17112998A JP4427109B2 JP 4427109 B2 JP4427109 B2 JP 4427109B2 JP 17112998 A JP17112998 A JP 17112998A JP 17112998 A JP17112998 A JP 17112998A JP 4427109 B2 JP4427109 B2 JP 4427109B2
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phosphorane
solution
hydrogenation
diphosphorane
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JPH11100393A (en
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シュテュルマー ライナー
ベルナー アーミン
ホルツ イェンス
フォス グードルン
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Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2423—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member comprising aliphatic or saturated rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
    • B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
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    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/44—Allylic alkylation, amination, alkoxylation or analogues
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    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

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  • Catalysts (AREA)

Description

【０００１】
【発明の属する技術分野】
本発明は、新規の光学活性ホスホラン及びビスホスホラン、その製造及び金属錯体中の配位子としての使用ならびにエナンチオ選択性合成への該金属錯体の使用に関する。
【０００２】
【従来の技術】
光学活性化合物の合成にとって、ロジウム及びルテニウム錯体を用いたエナンチオ選択性の水素化及び異性化は、重要な役割を果たしている（例えばTani他, J. Am. Chem. Soc 106, 5211, 1984； R. Noyori, Acc. Chem. Res. 23, 345 (1990)）。化学量論量の使用物質即ち水素は、安価であるが、しかしながら、使用される、通常光学活性のジホスフィン配位子及びロジウム又はルテニウム化合物から製造される触媒は、著しく高価でありかつ入手がきわめて困難である。光学活性ホスフィン及びジホスフィンの公知の製造方法は、全て複雑であり、かつ通常、技術的な困難及び高価なラセミ化合物分解を含む（例えば欧州特許出願公開第０６１４９０１号明細書； 欧州特許出願公開第０２７１３１１号明細書； H.B. Kagan, "Chiral Ligands for Asymmetric Catalysis" in Asymmetric Synthesis, 第5巻 (1985), 13〜23頁、欧州特許出願公開第０１５１２８２号明細書； 欧州特許出願公開第０１８５８８２号明細書； R. Noyori, Acc. Chem. Res. 23, 345 (1990)； 欧州特許出願公開第２６９３９５号明細書； M.J. Burk, Tetrahedron, Asymmetry, 569〜592頁 (1991)； J. Am. Chem. Soc. 113, 8518〜9頁 (1991)、同文献115, 10125〜138頁 (1993) 、同文献117, 9375〜76頁 (1995) 、同文献118, 5142頁 (1996)）。この欠点は、工業的な利用を困難かつ非経済的にする。
【０００３】
【発明が解決しようとする課題】
従って本発明の課題は、容易かつコスト的に有利に製造することができかつエナンチオ選択性合成のための金属錯体触媒のための良好な配位子であるホスフィン配位子を提供することであった。
【０００４】
【課題を解決するための手段】
特に効率的な種類の配位子、特にホスホランが「キラルプール(Chiral Pool)」から得られることが見いだされた。この出発材料は、この場合には、安価で大量に使用しうるマンニトール及び他の炭水化物である。
【０００５】
得られたホスホラン及びジホスホランは、不斉水素化の場合に著しいエナンチオマー過剰量をもたらす。ブルク(Burk)他によるＤＵＰＨＯＳ−配位子(DUPHOS - Liganden)(M.J. Burk, Tetrahedron, Asymmetry, 569〜592頁 (1991)； J. Am. Chem. Soc. 113, 8518〜9頁 (1991)、同文献115, 10125〜138頁 (1993) 、同文献117, 9375〜76頁 (1995) 、同文献118, 5142頁 (1996))は、公知であり、このＤＵＰＨＯＳ−配位子は、本発明とは異なり、合成するのはきわめて困難である。ＤＵＰＨＯＳ−配位子の合成のために不斉水素化の他にとりわけ、非実用的な電解によるフラスコ内の合成が必要である。
【０００６】
本発明は、上記問題点を、天然の源からエナンチオマー純粋に提供されうる糖即ちマンニトールの使用によって回避する。さらにこの抽出物は、ホスホラン環で３位及び４位で置換されている構造類似体、即ち公知のＤＵＰＨＯＳ−合成(DUPHOS-Synthese)で製造することができない類似体を得るための手段である。
【０００７】
本発明の対象は、一般式Ｉ：
【０００８】
【化５】

Figure 0004427109
【０００９】
〔式中、
Ｒ1及びＲ2は相互に無関係にＣ1〜Ｃ6−アルキル、アリール又はアルキルアリールを表わすか、又は
Ｒ1はさらに水素原子を表わし、
ＡはＲ1又は
【００１０】
【化６】
Figure 0004427109
【００１１】
（但しＢは２つのＰ原子間のＣ原子１〜５個を有する橋員を表わす）を表わす〕で示されるホスホラン及びジホスホランである。
【００１２】
有利な置換基Ｒ1及びＲ2はメチル、エチル、ｎ−プロピル、イソプロピル、 ｎ−ブチル、イソブチル、ｔ−ブチル、ベンジルである。
【００１３】
さらにこのような基Ｒ1は、２つのＲ1が一緒になって、イソプロピリデン又はベンジリデンを表わす。
【００１４】
ジホスホランの場合には、有利にＢが
【００１５】
【化７】
Figure 0004427109
【００１６】
〔但しｎは０、１、２、３又は４を表わす〕又は
【００１７】
【化８】
Figure 0004427109
【００１８】
〔但しｎは０、１、２又は３を表わし、
Ｒ3はアルキル又は縮合アリールを表わす〕
であるジホスホランである。
【００１９】
ｎが１又は２であるか或いはｍが０である橋員Ｂは、特に有利である。
【００２０】
本発明の別の対象は、上記ホスホランからの金属錯体である。
【００２１】
特に有利な金属錯体は、中心原子としてルテニウム又はロジウムを含有しているものである。この錯体は、公知方法（例えばUson, Inorg. Chim. Acta 73, 275 (1983)、欧州特許出願公開第０１５８８７５号明細書、欧州特許出願公開第４３７６９０号明細書）で、反応活性配位子を有するロジウム錯体、ルテニウム錯体、パラジウム錯体、白金錯体；ニッケル錯体（例えば[ＲｕＣｌ2(ＣＯＤ)]n、Ｒｈ(ＣＯＤ) 2ＢＦ4、 Ｒｈ(ＣＯＤ) 2ＣｌＯ4、[Ｉｒ2(ＣＯＤ)Ｃｌ]2、ｐ−シメン−ルテニウムクロリド−二量体）との反応によって触媒活性錯体が合成されることによって、製造することができる。
【００２２】
本発明の別の対象は、不斉合成の際の上記金属錯体の使用、特に水素化、ヒドロホルミル化、ヒドロシアン化、アリル置換及びエナミンへのアリルアミンの異性化のための触媒としての使用である。
【００２３】
上記の反応は、本発明による金属錯体を用いて、当業者に常用の条件下で実施することができる。
【００２４】
本発明による金属錯体を用いた水素化は、通常、温度−２０〜１５０℃、特に０〜１００℃、殊に１５〜４０℃で実施される。
【００２５】
水素圧は、０．１バール〜３００バールの広い範囲内で本発明による水素化方法について変動することができる。１〜１０バール、特に１〜２バールの圧力範囲内で著しく良好な性質が得られる。
【００２６】
本発明による配位子の場合には１〜２バールの低い水素圧は、特に有利であり、このような水素圧の場合には水素化は、著しく効率的に実施することができる。
【００２７】
【実施例】
例 １
テトラベンジルオキシ−Ｍｅ−ＤＵＰＨＯＳの製造
１，２；５，６−ジ−Ｏ−イソプロピリデン−Ｄ−マンニトール（１）： フルカ社(FLUKA)商品（注文番号３８４１０）。
【００２８】
【化９】
Figure 0004427109
【００２９】
３，４−ジ−Ｏ−ベンジル−１，２；５，６−ジ−Ｏ−イソプロピリデン−Ｄ−マンニトール（２）： J. Jurcak, T. Bauer, M. Chmielewski著, Carbohydr. Res. 164 (1987) 493に従って製造した。
【００３０】
【化１０】
Figure 0004427109
【００３１】
３，４−ジ−Ｏ−ベンジル−Ｄ−マンニトール（３）： J. Jurcak, T. Bauer, M. Chmielewski著, Carbohydr. Res. 164 (1987) 493に従って製造した。
【００３２】
【化１１】
Figure 0004427109
【００３３】
３，４−ジ−Ｏ−ベンジル−１，６−ジ−Ｏ−トルエンスルホニル−Ｄ−マンニトール（４）： J. Fittremann, A. Dureault, J.-C. Depezay著, Tetrahedron Letters 35 (1994) 1201に従って製造した。
【００３４】
【化１２】
Figure 0004427109
【００３５】
（２Ｒ，３Ｒ，４Ｒ，５Ｒ）−３，４−ジベンジルオキシ−ヘキサン−２，５−ジオール（５）： ＴＨＦ３０ｍｌ中のジトシレート４ １０ｇ（１４．９ｍモル）からなる溶液をＴＨＦ１００ｍｌ中のＬｉＡｌＨ4 ２．２５ｇ（５９．６ｍモル）の懸濁液に室温で徐々に滴加する。１時間の撹拌後に懸濁液を還流下に２時間加熱する。冷却後にこの水素化物を、水２．２５ｍｌ、１５％のＮａＯＨ２．２５ｍｌ及び再度水６．７５ｍｌを注意深く順番に添加することによって分解する。溶液から沈殿した無機化合物を濾別し、かつこの残留物を塩化メチレンでソックスレー抽出器で抽出する。合わせた溶液を乾燥させかつ、溶剤の蒸発除去後に残留物をカラムクロマトグラフィーによって精製する。（ｎ−ヘキサン：ＡｃＯＥｔ＝１：２、Ｒf＝０．４５）。
【００３６】
収量： ３．６ｇ（７３％）、白色固体。融点＝４６〜５０℃。
【００３７】
【外１】
Figure 0004427109
【００３８】
【化１３】
Figure 0004427109
【００３９】
（４Ｒ，５Ｒ，６Ｒ，７Ｒ）−５，６−ジベンジルオキシ４，７−ジメチル−［１，３，２］ジオキサチオパン２，２−ジオキシド（６）： ジオール５ ４．７５ｇ（１４．４ｍモル）をテトラクロロ炭化水素２０ｍｌ中で塩化チオニル１．３ｍｌとともに還流下に１．５時間加熱する。冷却後に溶剤を回転蒸発器で除去し、得られた残留物をテトラクロロ炭化水素１０ｍｌ、アセトニトリル１０ｍｌ及び水１５ｍｌで吸収する。０℃に冷却した溶液にＲｕＣｌ3・３Ｈ2Ｏ０．０２１ｇ（０．０８ｍモル）及び引き続き過ヨウ素酸ナトリウム６．２ｇ（２９．０ｍモル）を添加する。室温で１時間の撹拌後に、溶液に水７５ｍｌを添加し、かつジエチルエーテル１００ｍｌ×４で抽出する。合わせた抽出物を飽和ＮａＣｌ溶液で１回洗浄し、引き続き、Ｎａ2ＳＯ4を用いて乾燥させ、かつ珪藻土を通して濾過する。このエーテル性溶液を蒸発濃縮し、かつ環状スルフェートをカラムクロマトグラフィーによって精製する（ｎ−ヘキサン：ＡｃＯＥｔ＝９：１、Ｒf＝０．２５）。
【００４０】
収量： ３．４ｇ（６０％）、白色結晶。融点＝９０〜９４℃。
【００４１】
【外２】
Figure 0004427109
【００４２】
【化１４】
Figure 0004427109
【００４３】
１，２−ビス（（２Ｓ，３Ｓ，４Ｓ，５Ｓ）−３，４−ジベンジルオキシ−２，５−ジメチル−ホスホルアニル）ベンゼン（７）： ＴＨＦ７０ｍｌ中の１，２−ビス（ホスファニル）ベンゼン０．５６４ｇ（３．９６ｍモル）の溶液にｎ−ＢｕＬｉ４．９５ｍｌ（７．９３ｍモル）（ヘキサン中１．６モル）を室温で滴加する。生じた黄色の透明な溶液をさらに２時間撹拌しかつ、引き続き、ＴＨＦ１５ｍｌ中の環状スルフェート６ ３．１１ｇ（７．９２ｍモル）の溶液を徐々に添加する。この際、赤味を帯びたオレンジ色に色が急変する。４時間後にさらにｎ−ＢｕＬｉ５．４５ｍｌ（８．７１ｍモル）を反応混合物中に変換し、かつ室温でさらに１６時間撹拌する。後処理のために、得られた赤色の溶液にメタノール３ｍｌを添加し、かつＴＨＦを真空下に除去する。残留物を塩化メチレン５０ｍｌで吸収し、かつ嫌気条件下で水（２０ｍｌ）で洗浄する。乾燥（ Ｎａ2ＳＯ4）及び溶剤の除去の後にクロマトグラフィーによる精製を行なう（ｎ−ヘキサン：ＡｃＯＥｔ＝９：１、Ｒf＝０．２）。
【００４４】
収率４２％の無色のシロップ。
【００４５】
【外３】
Figure 0004427109
【００４６】
【化１５】
Figure 0004427109
【００４７】
（ＣＯＤ）Ｒｈ（１，２−ビス（（２Ｓ，３Ｓ，４Ｓ，５Ｓ）−３，４−ジベンジルオキシ−２，５−ジメチル−ホスホルアニル）ベンゼン（８）： ＴＨＦ３ｍｌ中のホスホラン７ ３００ｍｌ（０．４１ｍモル）の溶液に１当量のＲｈ(ＣＯＤ) 2ＢＦ4（１６７ｍｇ）を添加しかつ室温で１時間撹拌する。引き続き、溶液にジエチルエーテル２０ｍｌを添加し、この際、暗褐色の油が分離する。上澄み溶液の分離除去後に残留物をジエチルエーテル（１０ｍｌ×３）で洗浄しかつ、引き続き真空下に乾燥する。この際、青色の粉末として所望の錯体が得られる。
【００４８】
収量２００ｍｇ（４７％）。
【００４９】
【外４】
Figure 0004427109
【００５０】
【化１６】
Figure 0004427109
【００５１】
１，２−ビス（（２Ｓ，３Ｓ，４Ｓ，５Ｓ）−３，４−ジベンジルオキシ−２，５−ジメチル−ホスホルアニル）ベンゼン（ボラン錯体）（１）： ＴＨＦ７０ｍｌ中の１，２−ビス（ホスホンアニル）エタン０．３９６ｇ（４．２１ｍモル）の溶液にｎ−ＢｕＬｉ ５．２６ｍｌ（８．４２ｍモル）（ヘキサン中１．６モル）を撹拌下に室温で滴加する。生じた黄色の透明な溶液をさらに２時間撹拌し、かつ引き続き、ＴＨＦ１５ｍｌ中に溶解された環状スルフェート（４Ｒ，５Ｒ，６Ｒ，７Ｒ）−５，６−ジベンジルオキシ−４，７−ジメチル−［１，３，２］ジオキサチエパン−２，２−ジオキシド）３．３０ｇ（７．９２ｍモル）を徐々に添加する。この際、黄褐色に色が急変する。４時間後にさらにｎ−ＢｕＬｉ５．７９ｍｌ（９．２６ｍモル）（１．６モル）を反応混合物中に変換し、かつ室温でさらに１６時間撹拌する。後処理のために、得られた透明な淡褐色の溶液を冷却し、かつ２．２当量のＢＨ3−ＴＨＦ複合体（１モル、９．２６ｍｌ）を添加する。２時間後に溶剤を除去し、残留物を水２０ｍｌで吸収し、かつ生成物を塩化メチレン（３０ｍｌ×３）で抽出する。蒸発濃縮後に、カラムクロマトグラフィー（ｎ−ヘキサン：ＡｃＯＥｔ＝４：１、Ｒf＝０．２５）による精製によって所望の生成物が、収量４８０ｍｇ（１６％）で得られる。
【００５２】
【外５】
Figure 0004427109
【００５３】
１，２−ビス（（２Ｓ，３Ｓ，４Ｓ，５Ｓ）−３，４−ジベンジルオキシ−２，５−ジメチル−ホスホルアニル）エタン（２）： 化合物１ ２９０ｍｇ（０．４１ｍモル）をトルエン１５ｍｌ中の３当量のＤＡＢＣＯとともに４０℃で撹拌する。ＤＣ（ｎ−ヘキサン：ＡｃＯＥｔ＝４：１、Ｒf＝０．３）において完全な変換が示された後に、カラムクロマトグラフィーによる後処理の後に、収率７５％（２１０ｍｇ）で化合物２が得られる。
【００５４】
【外６】
Figure 0004427109
【００５５】
Ｒｈ［１，２−ビス（（２Ｓ，３Ｓ，４Ｓ，５Ｓ）−３，４−ジベンジルオキシ−２，５−ジメチル−ホスホルアニル）エタン］［ＣＯＤ］テトラフルオロボレート（３）： ＴＨＦ３ｍｌ中のビスホスホラン２ １８０ｍｇ（０．２６ｍモル）の溶液に１当量の［Ｒｈ（ＣＯＤ）2］ＢＦ4（１０７ｍｇ）を添加し、かつ室温で１時間撹拌する。引き続き、この溶液にジエチルエーテル１５ｍｌを添加し、この際、暗褐色の油が分離する。上澄み溶液の分離除去後に粘稠な残留物をジエチルエーテル（１０ｍｌ×３）で洗浄し、この際、固体沈殿物が形成される。引き続き、この沈殿物を真空下に乾燥する。この際、オレンジ色を帯びた褐色の粉末として所望の錯体が収量１３４ｍｇ（５２％）で得られる。
【００５６】
【外７】
Figure 0004427109
【００５７】
例 ２
不斉水素化のための典型的方法
ロス(Roth)社の実験室用オートクレーブ中に保護ガス雰囲気下にＭｅＯＨ中の触媒０．０１ｍモルを装入し、この混合物に基質１０ｍモルを添加し、かつ１バールの水素圧及び室温で水素化する。結果及び水素化時間は、次の表に示されているとおりである。
【００５８】
水素化の結果
条件： ２５℃、Ｈ2 １バール、基質１０ｍモル、例１によるＲｈ−触媒（８）０．０１モル％、 ＭｅＯＨ
【００５９】
【表１】
Figure 0004427109
【００６０】
分析：
プロキラル酸ＡＨ及びないしはＩｔＨ２を水素化した場合には、少量（溶液約１ｍｌ）をジアゾメタンないしはトリメチルシリルジアゾメタンでエステル化した。全ての水素化反応の、存在するメチルエステルを次のとおり分析した：
Figure 0004427109
【００６１】
不斉水素化
条件： Ｈ2 １バール、 ＭｅＯＨ１５ｍｌ 、２５℃、基質１０ｍモル、触媒（３）０．０１ｍモル；
ＡＨ： ９３．１％ｅｅ （Ｓ）−生成物 ｔ1／ｔ2＝３１分
ＡＭｅ： ９７．５％ｅｅ （Ｓ）−生成物 ｔ1／ｔ2＝２６分。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to novel optically active phospholanes and bisphospholanes, their preparation and use as ligands in metal complexes and the use of the metal complexes for enantioselective synthesis.
[0002]
[Prior art]
For the synthesis of optically active compounds, enantioselective hydrogenation and isomerization using rhodium and ruthenium complexes plays an important role (eg Tani et al., J. Am. Chem. Soc 106, 5211, 1984; R Noyori, Acc. Chem. Res. 23, 345 (1990)). The stoichiometric amount of the substance used, ie hydrogen, is inexpensive, however, the catalysts used, usually made from optically active diphosphine ligands and rhodium or ruthenium compounds, are extremely expensive and highly available. Have difficulty. Known processes for the production of optically active phosphines and diphosphines are all complex and usually involve technical difficulties and expensive racemate decomposition (eg EP-A-0614901; EP-A-0271311 HB Kagan, “Chiral Ligands for Asymmetric Catalysis” in Asymmetric Synthesis, Vol. 5 (1985), 13-23, European Patent Application Publication No. 0151582; European Patent Application Publication No. 0185882; R. Noyori, Acc. Chem. Res. 23, 345 (1990); European Patent Application No. 269395; MJ Burk, Tetrahedron, Asymmetry, pages 569-592 (1991); J. Am. Chem. Soc. 113, 8518-9 (1991), 115, 10125-138 (1993), 117, 9375-76 (1995), 118, 5142 (1996). This disadvantage makes industrial use difficult and uneconomical.
[0003]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a phosphine ligand that can be easily and cost-effectively produced and is a good ligand for a metal complex catalyst for enantioselective synthesis. It was.
[0004]
[Means for Solving the Problems]
It has been found that a particularly efficient class of ligands, in particular phosphoranes, can be obtained from the “Chiral Pool”. The starting materials are in this case mannitol and other carbohydrates that are inexpensive and can be used in large quantities.
[0005]
The resulting phospholanes and diphosphoranes result in a significant enantiomeric excess in the case of asymmetric hydrogenation. DUPHOS-Liganden by Burk et al. (MJ Burk, Tetrahedron, Asymmetry, pages 569-592 (1991); J. Am. Chem. Soc. 113, pages 8518-9 (1991), 115, 10125-138 (1993), 117, 9375-76 (1995), 118, 5142 (1996)), and this DUPHOS-ligand is the present invention. Unlike, it is very difficult to synthesize. In addition to asymmetric hydrogenation for the synthesis of DUPHOS-ligands, inter alia synthesis in flasks by impractical electrolysis is necessary.
[0006]
The present invention avoids the above problems by the use of a sugar or mannitol that can be provided enantiomerically pure from natural sources. Furthermore, this extract is a means for obtaining structural analogs substituted at the 3- and 4-positions on the phosphorane ring, ie analogs that cannot be prepared by the known DUPHOS-Syntheses.
[0007]
The subject of the present invention is the general formula I:
[0008]
[Chemical formula 5]
Figure 0004427109
[0009]
[Where,
R 1 and R 2 independently of one another represent C 1 -C 6 -alkyl, aryl or alkylaryl, or R 1 further represents a hydrogen atom,
A is R 1 or [0010]
[Chemical 6]
Figure 0004427109
[0011]
(Wherein B represents a bridge member having 1 to 5 C atoms between two P atoms)].
[0012]
Preferred substituents R 1 and R 2 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, benzyl.
[0013]
Furthermore, such a group R 1 , together with two R 1 , represents isopropylidene or benzylidene.
[0014]
In the case of diphosphorane, B is preferably
[Chemical 7]
Figure 0004427109
[0016]
[N represents 0, 1, 2, 3 or 4] or
[Chemical 8]
Figure 0004427109
[0018]
[Where n represents 0, 1, 2 or 3;
R 3 represents alkyl or fused aryl]
Is a diphosphorane.
[0019]
The bridge member B in which n is 1 or 2 or m is 0 is particularly advantageous.
[0020]
Another subject of the invention is a metal complex from the above phosphorane.
[0021]
Particularly advantageous metal complexes are those containing ruthenium or rhodium as the central atom. This complex is obtained by a known method (for example, Uson, Inorg. Chim. Acta 73, 275 (1983), European Patent Application Publication No. 0158875, European Patent Application Publication No. 437690) and a reactive ligand. Rhodium complex, ruthenium complex, palladium complex, platinum complex; nickel complex (for example, [RuCl 2 (COD)] n , Rh (COD) 2 BF 4 , Rh (COD) 2 ClO 4 , [Ir 2 (COD) Cl] 2 , p-cymene-ruthenium chloride-dimer) can be produced by synthesizing a catalytically active complex.
[0022]
Another subject of the present invention is the use of the above metal complexes in asymmetric synthesis, in particular as catalysts for hydrogenation, hydroformylation, hydrocyanation, allyl substitution and isomerization of allylamines to enamines.
[0023]
The above reaction can be carried out under conditions commonly used by those skilled in the art using the metal complex according to the present invention.
[0024]
The hydrogenation using the metal complex according to the invention is usually carried out at temperatures from -20 to 150 ° C, in particular from 0 to 100 ° C, in particular from 15 to 40 ° C.
[0025]
The hydrogen pressure can be varied for the hydrogenation process according to the invention within a wide range from 0.1 bar to 300 bar. Very good properties are obtained within a pressure range of 1 to 10 bar, in particular 1 to 2 bar.
[0026]
In the case of the ligands according to the invention, a low hydrogen pressure of 1 to 2 bar is particularly advantageous, in which case the hydrogenation can be carried out very efficiently.
[0027]
【Example】
Example 1
Preparation of tetrabenzyloxy-Me-DUPHOS 1,2; 5,6-di-O-isopropylidene-D-mannitol (1): FLUKA product (order number 38410).
[0028]
[Chemical 9]
Figure 0004427109
[0029]
3,4-di-O-benzyl-1,2; 5,6-di-O-isopropylidene-D-mannitol (2): by J. Jurcak, T. Bauer, M. Chmielewski, Carbohydr. Res. 164 (1987) 493.
[0030]
[Chemical Formula 10]
Figure 0004427109
[0031]
3,4-Di-O-benzyl-D-mannitol (3): Prepared according to J. Jurcak, T. Bauer, M. Chmielewski, Carbohydr. Res. 164 (1987) 493.
[0032]
Embedded image
Figure 0004427109
[0033]
3,4-Di-O-benzyl-1,6-di-O-toluenesulfonyl-D-mannitol (4): by J. Fittremann, A. Dureault, J.-C. Depezay, Tetrahedron Letters 35 (1994) Produced according to 1201.
[0034]
Embedded image
Figure 0004427109
[0035]
(2R, 3R, 4R, 5R) -3,4-dibenzyloxy-hexane-2,5-diol (5): A solution consisting of 10 g (14.9 mmol) of ditosylate 4 in 30 ml of THF is LiAlH 4 in 100 ml of THF. Gradually add dropwise to 2.25 g (59.6 mmol) of suspension at room temperature. After stirring for 1 hour, the suspension is heated under reflux for 2 hours. After cooling, the hydride is destroyed by careful sequential addition of 2.25 ml water, 2.25 ml 15% NaOH and again 6.75 ml water. The inorganic compound precipitated from the solution is filtered off and the residue is extracted with methylene chloride in a Soxhlet extractor. The combined solution is dried and after evaporation of the solvent, the residue is purified by column chromatography. (N-hexane: AcOEt = 1: 2, Rf = 0.45).
[0036]
Yield: 3.6 g (73%), white solid. Melting point = 46-50 ° C.
[0037]
[Outside 1]
Figure 0004427109
[0038]
Embedded image
Figure 0004427109
[0039]
(4R, 5R, 6R, 7R) -5,6-Dibenzyloxy 4,7-dimethyl- [1,3,2] dioxathiopane 2,2-dioxide (6): 4.75 g of diol 5 (14.4 mmol) ) In 20 ml tetrachlorohydrocarbon with 1.3 ml thionyl chloride at reflux for 1.5 hours. After cooling, the solvent is removed on a rotary evaporator and the residue obtained is taken up with 10 ml of tetrachlorohydrocarbon, 10 ml of acetonitrile and 15 ml of water. To the solution cooled to 0 ° C., 0.021 g (0.08 mmol) of RuCl 3 .3H 2 O and subsequently 6.2 g (29.0 mmol) of sodium periodate are added. After stirring for 1 hour at room temperature, 75 ml of water is added to the solution and extracted with 100 ml × 4 diethyl ether. The combined extracts are washed once with saturated NaCl solution, subsequently dried with Na 2 SO 4 and filtered through diatomaceous earth. The ethereal solution is concentrated by evaporation and the cyclic sulfate is purified by column chromatography (n-hexane: AcOEt = 9: 1, R f = 0.25).
[0040]
Yield: 3.4 g (60%), white crystals. Melting point = 90-94 ° C.
[0041]
[Outside 2]
Figure 0004427109
[0042]
Embedded image
Figure 0004427109
[0043]
1,2-bis ((2S, 3S, 4S, 5S) -3,4-dibenzyloxy-2,5-dimethyl-phosphoranyl) benzene (7): 1,2-bis (phosphanyl) benzene 0 in 70 ml of THF To a solution of .564 g (3.96 mmol) n-BuLi 4.95 ml (7.93 mmol) (1.6 mol in hexane) is added dropwise at room temperature. The resulting yellow clear solution is stirred for another 2 hours and subsequently a solution of 3.11 g (7.92 mmol) of cyclic sulfate 6 in 15 ml of THF is slowly added. At this time, the color suddenly changes to reddish orange. After 4 hours, a further 5.45 ml (8.71 mmol) of n-BuLi are converted into the reaction mixture and stirred at room temperature for a further 16 hours. For workup, 3 ml of methanol are added to the resulting red solution and the THF is removed in vacuo. The residue is taken up with 50 ml of methylene chloride and washed with water (20 ml) under anaerobic conditions. Drying (Na 2 SO 4 ) and removal of the solvent are followed by chromatographic purification (n-hexane: AcOEt = 9: 1, R f = 0.2).
[0044]
42% colorless syrup in yield.
[0045]
[Outside 3]
Figure 0004427109
[0046]
Embedded image
Figure 0004427109
[0047]
(COD) Rh (1,2-bis ((2S, 3S, 4S, 5S) -3,4-dibenzyloxy-2,5-dimethyl-phosphoranyl) benzene (8): 300 ml of phosphorane 7 in 3 ml of THF (0 1 equivalent of Rh (COD) 2 BF 4 (167 mg) to a solution of .41 mmol) and stirred for 1 hour at room temperature, followed by addition of 20 ml of diethyl ether to the solution, with a dark brown oil After separating off the supernatant solution, the residue is washed with diethyl ether (10 ml × 3) and subsequently dried under vacuum, giving the desired complex as a blue powder.
[0048]
Yield 200 mg (47%).
[0049]
[Outside 4]
Figure 0004427109
[0050]
Embedded image
Figure 0004427109
[0051]
1,2-bis ((2S, 3S, 4S, 5S) -3,4-dibenzyloxy-2,5-dimethyl-phosphoranyl) benzene (borane complex) (1): 1,2-bis (70 ml in THF) To a solution of 0.396 g (4.21 mmol) of phosphonyl) ethane, 5.26 ml (8.42 mmol) of n-BuLi (1.6 mol in hexane) is added dropwise at room temperature with stirring. The resulting yellow clear solution is stirred for a further 2 hours and subsequently cyclic sulfate (4R, 5R, 6R, 7R) -5,6-dibenzyloxy-4,7-dimethyl- [ 1,3,2] dioxathiepan-2,2-dioxide) 3.30 g (7.92 mmol) is slowly added. At this time, the color suddenly changes to yellowish brown. After 4 hours, a further 5.79 ml (9.26 mmol) (1.6 mol) of n-BuLi are converted into the reaction mixture and stirred at room temperature for a further 16 hours. For workup, the resulting clear light brown solution is cooled and 2.2 equivalents of BH3 -THF complex (1 mol, 9.26 ml) are added. After 2 hours the solvent is removed, the residue is taken up with 20 ml of water and the product is extracted with methylene chloride (30 ml × 3). After evaporation, purification by column chromatography (n-hexane: AcOEt = 4: 1, R f = 0.25) gives the desired product in a yield of 480 mg (16%).
[0052]
[Outside 5]
Figure 0004427109
[0053]
1,2-bis ((2S, 3S, 4S, 5S) -3,4-dibenzyloxy-2,5-dimethyl-phosphoranyl) ethane (2): 290 mg (0.41 mmol) of compound 1 in 15 ml of toluene Stir at 40 ° C. with 3 equivalents of DABCO. Compound 2 was obtained in 75% yield (210 mg) after work-up by column chromatography after complete conversion was shown in DC (n-hexane: AcOEt = 4: 1, R f = 0.3). It is done.
[0054]
[Outside 6]
Figure 0004427109
[0055]
Rh [1,2-bis ((2S, 3S, 4S, 5S) -3,4-dibenzyloxy-2,5-dimethyl-phosphoranyl) ethane] [COD] tetrafluoroborate (3): bisphospholane in 3 ml of THF 2 Add 1 equivalent of [Rh (COD) 2 ] BF 4 (107 mg) to 180 mg (0.26 mmol) of solution and stir at room temperature for 1 hour. Subsequently, 15 ml of diethyl ether are added to this solution, with a dark brown oil separating. After separating off the supernatant solution, the viscous residue is washed with diethyl ether (10 ml × 3), whereupon a solid precipitate is formed. Subsequently, the precipitate is dried under vacuum. In this case, the desired complex is obtained in a yield of 134 mg (52%) as an orange-brown powder.
[0056]
[Outside 7]
Figure 0004427109
[0057]
Example 2
Typical Method for Asymmetric Hydrogenation A Roth laboratory autoclave was charged with 0.01 mmol of catalyst in MeOH under a protective gas atmosphere and 10 mmol of substrate was added to the mixture. And hydrogenation at 1 bar hydrogen pressure and room temperature. The results and hydrogenation times are as shown in the following table.
[0058]
Resulting conditions of hydrogenation: 25 ° C., 1 bar of H 2 , 10 mmol of substrate, Rh-catalyst according to example 1 (8) 0.01 mol%, MeOH
[0059]
[Table 1]
Figure 0004427109
[0060]
analysis:
When the prochiral acid AH and / or ItH2 was hydrogenated, a small amount (about 1 ml of solution) was esterified with diazomethane or trimethylsilyldiazomethane. The methyl esters present in all hydrogenation reactions were analyzed as follows:
Figure 0004427109
[0061]
Asymmetric hydrogenation conditions: H 2 1 bar, MeOH 15 ml, 25 ° C., substrate 10 mmol, catalyst (3) 0.01 mmol;
AH: 93.1% ee (S) -product t 1 / t 2 = 31 min AMe: 97.5% ee (S) -product t 1 / t 2 = 26 min.

Claims (7)

一般式Ｉ：
Figure 0004427109
〔式中、
Ｒ1 はベンジルを表し、及びＲ2 はＣ 1〜Ｃ6−アルキル、アリール又はアルキルアリールを表わし、
Ａは
Figure 0004427109
（但しＢは
Figure 0004427109
〔但しｎは０、１、２、３又は４を表わす〕又は
Figure 0004427109
〔但しｍは０、１、２又は３を表わし、
Ｒ3はアルキルを表わす〕
を表わす）を表わす〕
で示されるホスホラン又はジホスホラン。Formula I:
Figure 0004427109
 [Where,
R 1 represents benzyl, and R 2 is C 1 -C 6 - alkyl, aryl or alkylaryl and Table Wa,
A is
Figure 0004427109
 (B is
Figure 0004427109
 [Wherein n represents 0, 1, 2, 3 or 4] or
Figure 0004427109
 [However, m represents 0, 1, 2, or 3;
R 3 represents alkyl le]
Represents)
A phosphorane or diphosphorane represented by ｍが０であるか、又はｎが１である、請求項１記載のジホスホラン。m is 0 der Luke, or n is 1, Jihosuhoran of claim 1, wherein. 請求項１又は２に記載のジホスホランとＲｈ、Ｒｕ、Ｉｒ、Ｐｄ、Ｐｔ、Ｎｉの群から選択された中心原子とからなる金属錯体。Claim 1 or 2 di phosphorane Rh described, Ru, Ir, Pd, Pt , metal complexes comprising a central atom selected from the group and Ni. 中心原子としてＲｈ又はＲｕが選択されている、請求項３記載の金属錯体。The metal complex according to claim 3 , wherein Rh or Ru is selected as a central atom. 化合物の不斉水素化の方法において、水素化すべき出発化合物を請求項３又は４に記載の金属錯体の存在下で水素と反応させることを特徴とする、化合物の不斉水素化の方法。A method for asymmetric hydrogenation of a compound, characterized in that a starting compound to be hydrogenated is reacted with hydrogen in the presence of the metal complex according to claim 3 or 4 . 水素化を水素圧１〜２バールで実施する、請求項５記載の方法。6. Process according to claim 5 , wherein the hydrogenation is carried out at a hydrogen pressure of 1 to 2 bar. 水素化すべき出発化合物が
Figure 0004427109
 であることを特徴とする、請求項５又は６記載の方法。 The starting compound to be hydrogenated is
Figure 0004427109
 The method according to claim 5 or 6, characterized in that
JP17112998A 1997-06-18 1998-06-18 Phosphorane and diphosphorane, metal complexes thereof, use thereof and method of asymmetric hydrogenation Expired - Lifetime JP4427109B2 (en)

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